Unsaturated 1, 3-glycols



Patented Apr. 1, 1947 UNITED STATES ausaao' PATENT OFFICE UNSATURATED 1,3-GLYCOLS Herman A. Bruson and Warren D. Niederhanser,

Philadelphia, Pa., asslgnors to l'he Besinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware v I IOCIalms.

This invention relates to unsaturated 1,8-glyl cols corresponding to the formula s-cn=cn-$-omon nion wherein R and R are hydrocarbon groups. It further relates to a method for the preparation of these glycois. a

We have found that ary-dlsiibbtltlltfid crotonaldehydes react with formaldehyde in the presence of a water-soluble fixed base to give glycols of the above formula. The reaction involves a transposition of the double bond, an addition to the a-carbon atom, and a reduction of the carbonyl group. The reaction may be represented by the equation R! I R! n-oHrcH=o-cno'+ mono melanoma-onion men Typical aq-dihydrocarbon substituted ci'otonaldehydes which are useful may be represented by the formula in which R and R are alkyl, aryl, arylalkyl, or

5 cycloalkyl groups. R is preferably an alkyl groupysuch as methyl, ethyl, propyl, butyl, hexyl, etc., but may also be a phenyl, substituted phenyl such as methylphenyl, tert.-butyipheny1, or similar group, or a benzyl, phenylethyl. cyclohexyl, methylcyclohexyl, or other substituent hydrocarbon group. B may similarly be any of these groups, particularly an alkyl group, which need not be the same as R. These ary-dlsllbstitlltBd crotonaldehydes. which may also. be considered acroleln derivatives, are obtainable by condensing together two molecules of the same aldehyde or a molecule of each of two different aldehydes by known methods which involve aldolization and elimination of water. When mixtures of unsaturated aldehydes are obtained, they may be separated into diflerent entities or, if desired. a mixture may be reacted with formaldehyde to give a mixture of glycols.

Representative of the aldehydes of the above formula are ary-dimethyl crotonaldehyde, c-ydiethyl crotonaldehyde, ,y-dibutyl crotonaldehyde. a-methyl-y-ethyl crotonaldehyde, a-methyl-v-phenyl crotonaldehyde, a-methyl-pbenzyl crotonaldehyde, a-methyl-y-cyclohexyl crotonaldehyde, a-ethyl-y-phenyl crotonaldehyde, and homologues thereof.

of an aqueous solution or slurry. It has been found desirable to use the fixed base in an amount at-least equivalent to the a;y-disubstituted a1de-.

hyde. A molecular excess appears in many cases to improve the yields. In the reaction products, the cation from the base is found in the form of a formate.

, The formaldehyde may be supplied by an auue-" one or organic solvent solution thereof or from a compound yielding formaldehyde under the conditions of the reaction, such as paraformaldehyde. Although two mols of formaldehyde per mol of a,- -disubstituted crotonaldehyde are theoretically required in the reaction, it has been found desirable to use a larger ratio to promote better yields. The reaction mixture may advantageously be "made with two and a half to four mole or even a larger excess of formaldehyde 80 per mol of the unsaturated aldehyde.

' The reaction of a,y-disubstituted crotonaldehyde with formaldehyde in the presence of a fixed base may be effected by heatlngat 50 to 110 C. An inert solvent,-such as ethyl alcohol.

' isopropyl alcohol, benzene, naphtha, or toluene.

may effectively be used and the reaction carried on under reflux conditions. Good stirring is advantageous, particularly where two liquid phases are at hand.

Specific details of typical preparation of the unsaturated 1-,3-s1ycols of this invention are given in the following examples. The parts given are by weight.

, Eramiile 1 crotonaldehyde, 489 parts of 36% aqueous formaldehyde, and 400 parts of ethyl alcohol was stirred and maintained at 86 C. by heatingwhile A solution containing 252 parts of a diethyl aeraseo oxide. The approximately neutral mixture washed with water and separated to give 253 parts of crude product, which, on distillation. gave 153'parts boiling at l15-135 C./ mm. On redlstillation, the fraction boiling at 150-152 C./21 mm. was a colorless, sweet-smelling liquid with a density, d4, of 0.9663 and a refractive index, a of 1.4751. Its structureis an. ouncm-on-d-cmon HiOH Example 2 A solution containing 48 parts of a,"y-diamyl I crotonaldehyde, 50 parts of 86% aqueous formaldehyde, and 80, parts of ethyl alcohol was stirred and maintained at 85 C. by heating while to it there was added 25 parts of a 50% aqueous solution of potassium hydroxide over a period of fifteen minutes. The reaction mixture was stirred under reflux at 83 C. for twenty one hours.

product which was washed with dilute formic acid and with water and dried on the steam bath under reduced pressure to give 39 parts'of pale yellow oil. This was distilled under reduced pressure to give 24 parts of a fraction boiling at 150-190 C./5 mm. On redistillation, the product came over at 165-170 C./5 mm. Its structure is e sKn ClEiiCBflCH--OBiH HrOK Example 3 A solution of 106 parts of sodium carbons. in 300 parts of water was added dropwise to a stirred mixture of 126 parts of sfl-diethyl crotonaldehyde, 245 parts of aqueous 37% formaldehyde, and 240 parts of 95% ethyl alcohol at 80 C. The resulting reaction mixture was heated under reflux for twenty hours at 80 to 95 C. The solvents were then removed by heating on a. steam bath under reduced pressure. The resulting product was washed and dried. There was obtained 97 parts of a dark oil which was distilled at low pressure. The fraction distilling this carbon atom. These dihydric alcohols are useful in the preparation of resins, for example with dibasic acids and/or fatty acids, and plasticizers. They are also useful as solvents.

We claim:

1. A method for preparing glycols oi the formula BI RCH=CH-i J-CH:OB

wherein R and R are each hydrocarbon groups, whi h comprises reacting together in the pres- Most of the alcohol was then distilled off under reduced pressure, leaving a residual ence of a water-soluble fixed base an afl-dihydrocarbon mibstltuted crotonaldehyde and formaldehyde.

2. A method for preparing glycols of the far- A a-c'n-cm-b-cmonmen wherein ,R and R are hydrocarbon groups, which comprises reactingtogether by heating at 50 C. v

to about C. in the presence of a water-soluble fixed base an a,'y-di-hydrocarbon substituted crotonaldehyde and formaldehyde.

3. A method for preparing glycols of the for- I mula I a a R-.CH=OH-(LCH|0H men wherein R and R. are hydrocarbon groups, whichfl comprises reacting together by heating at 50 C. to about 110- C. in an organic solvent and in the presence of an alkali hydroxide an U, Y"di" hydrocarbon substituted crotonaldehyde and formaldehyde.

4. A method for preparing glyools of the formula l n-cn=c'n-c-cmon mon wherein R and R are hydrocarbon groups, which comprises reacting together at 50 C. to about 110 C. in the presence of a water-soluble fixed base and water one moi of an ,'y-dihydrocarbon substituted crotonaldehyde and at least two mols of formaldehyde,

5. A method for preparing glycols of the formula wherein R and R are hydrocarbon groups, which comprises reacting together at about 50 C. to: about 110 C. one molecular equivalent of an (y-3 dihydrocarbon substituted crotonaldehyde, a molecular equivalent of a water-soluble fixed base, and two molecular equivalents of formaldehyde.

6. A method for preparing formula RI R-cH==cH :cHi0H I HzO-H wherein R. and R are alkyl groups, which comprises reacting together at about 50 C. to about 110 C. one molecular equivalent of an cry-dialkyl crotonaldehyde, a molecular equivalent of glycols of the a soluble inorganic hydroxide, and two molecular equivalents of formaldehyde.

'7. A method for preparing glycols of the formula R! a-on=oa-o-omon moi:

wherein R and R are alkyl groups, which comprises reacting together at about 50 C. to about 110 C. one molecular equivalent of an-m'y-dialkyl crotonaldehyde, a molecular equivalent of an alkali carbonate. and two molecular lents of formaldehyde.

- wherein R and R are slkyl groups, which comprises mixing and heating together at 50' to about 110' C. 1n the presence of water one moleculsr equivalent of en aky-dlalkyl crotonnldehyde. at least one molecular equivalent of a. strong inorzanlc hydroxide, and at least two molecular equivalents of formaldehyde. I

9.A method for prepsrlm a ll'ycolzof the formula I' cmcmon-on men 6 which comprises reacting, tocether at about 50 C. to about 110' C. in the presence of a, strongly elksllne hydroxide ,-y-dlethy1 crotoneldehyde and an excess of formaldehyde.

10. As a new compound, the unsaturated glycol havlnz the formula an omcnr-on=cno-cmon mon HERMAN A. BRUBON. WARREN D. NIEDIRHAUSER.

' REFERENCES CITED The following references are of record in the mo-o! thlsnetent: r

Yugo. I'ormoldehyde. pp 160-188. (Cow 

